Styling shampoo compositions with improved styling polymer deposition

ABSTRACT

Disclosed are hair styling shampoo compositions which comprise from about 5% to about 50% by weight of a surfactant selected from the group consisting of anionic surfactants, zwitterionic or amphoteric surfactants having an attached group that is anionic at the pH of the composition, and combinations thereof; from about 0.025% to about 3% by weight of an organic cationic polymer having a cationic charge density of from about 0.2 meq/gm to about 7 meq/gm and a molecular weight of from about 5,000 to about 10 million; from about 0.1% to about 10% by weight of a water-insoluble hair styling polymer; from about 0.1% to about 10% by weight of a water-insoluble volatile solvent; and from about 0.05% to about 5% by weight of select cationic materials for use as spreading agents for the styling polymer; and from about 22% to about 94.3% by weight water. The composition provides improved spreading efficiency of the styling polymer onto hair, thus providing improved styling performance from the shampoo composition.

FIELD OF THE INVENTION

The present invention relates to hair styling shampoo compositions whichprovide improved styling performance. More particularly, the presentinvention relates to styling shampoo compositions which contain acationic deposition polymer and select spreading agents to improve thestyling performance.

BACKGROUND OF THE INVENTION

Many hair shampoo compositions provide acceptable cleaning but providelittle or no styling benefits, e.g. body, hold, stiffness. To realizesuch benefits, separate cleaning and styling products are often used.

Recently, hair shampoo compositions have been developed which canprovide cleaning and styling performance from a single product. Many ofthese products contain styling polymers in a compatible shampoo base. Toprepare such products, styling polymers can be dissolved in an organicsolvent and then incorporated into the shampoo base. The organic solventthereafter helps disperse the styling polymer in the shampoocomposition, and also helps enhance spreading of the styling polymeronto hair such that the polymer sets and forms a thin film onto thesurface of the hair shaft. The enhanced spreading of the styling polymeronto the hair results in improved styling performance from the shampoocomposition.

Another method for further improving polymer deposition from a shampooinvolves the use of cationic deposition polymers. These cationicdeposition polymers improve the deposition efficiency of the stylingpolymers, which in turn also improves styling performance. The improveddeposition from the cationic polymer can also allow for reduction of theamount of styling polymer formulated into the shampoo composition, thusreducing raw material costs. Cationic deposition polymers, however, cancause compatibility problems with other materials in the formulation,especially when used at higher concentrations or at relatively highcationic charge densities. Moreover, excessive amounts of suchdeposition polymers can result in undesirably slick or oily wet hairfeel, and can cause the hair when dry to feel dirty and have less body,less fullness.

It has now been found that these water-insoluble styling polymers involatile solvents can be rendered more effective, and potentially usedat lower concentrations, when used in combination with select cationicspreading agents. It has also been found that the select cationicspreading agents provide this deposition benefit only when used incombination with these cationic deposition polymers. It is believed thatthe select cationic spreading agents help reduce surfactant micelle sizein the shampoo composition, which either forces more of the volatilesolvent out of the micelle or prevents the initial solubilization of thevolatile solvent into the micelle to make it more readily available tohelp deposit and spread the styling polymer onto the hair. Moreover,more volatile solvent for the styling polymer is being deposited withthe styling polymer, thus resulting in a less viscous droplet whichspreads better. This improves the character or mophology of the depositof the styling polymer onto the hair, while also allowing for minimalconcentrations of cationic deposition polymer to be present in thecomposition.

In view of the foregoing, it is therefore an object of the presentinvention to provide a styling shampoo composition with improved stylingperformance. It is a further object of the present invention to improvethe spreading efficiency of styling polymer from a shampoo compositioncontaining a cationic deposition polymer, and further to provide for theimproved spreading efficiency using select cationic spreading agents incombination with a water-insoluble styling polymer and a volatilesolvent for the styling polymer.

SUMMARY OF THE INVENTION

The present invention is directed to hair styling shampoo compositionswhich comprise from about 5% to about 50% by weight of a surfactantselected from the group consisting of anionic surfactants, zwitterionicor amphoteric surfactants having an attached group that is anionic atthe pH of the composition, and combinations thereof; from about 0.025%to about 3% by weight of an organic cationic polymer having a cationiccharge density of from about 0.2 meq/gm to about 7 meq/gm and amolecular weight of from about 5,000 to about 10 million; from about0.1% to about 10% by weight of a water-insoluble hair styling polymer;from about 0.1% to about 10% by weight of a solvent having a boilingpoint of less than about 300° C. and a water solubility at 25° C. ofpreferably less than about 0.2% by weight; and from about 0.05% to about5% by weight of a non-polymeric, cationic spreading agent; and fromabout 22% to about 94.3% by weight of water.

It has been found that the shampoo composition of the present inventionprovides improved spreading efficiency of the styling polymer onto hair,thus providing improved styling performance from the shampoocomposition. It has been found that the cationic spreading agent, whenused in combination with the cationic deposition polymer,water-insoluble styling polymer, water-insoluble volatile solvent, andanionic surfactant, provides for improved spreading of thewater-insoluble styling polymer on hair relative to comparableformulations that do not contain the cationic compound. It is believedthat more volatile solvent is deposited with the water insoluble stylingpolymer onto the hair, but only to the extent that the solvent isavailable outside the surfactant micelle during the shampooing andrinsing process. It is believed that the cationic spreading agentinhibits the solubilization of the volatile solvent into the surfactantmicelles, thus providing more volatile solvent outside the surfactantmicelles to help with improved spreading of the styling polymer ontohair. The improved spreading of the polymer then results in improvedstyling performance.

DETAILED DESCRIPTION OF THE INVENTION

The shampoo compositions of the present invention can comprise, consistof, or consist essentially of the essential elements and limitations ofthe invention described herein, as well any of the additional oroptional ingredients, components, or limitations described herein.

As used herein, the term “water-insoluble” refers to any material thathas a solubility in water at 25° C. of less than about 0.5%, preferablyless than about 0.3%, even more preferably less than about 0.2% byweight.

All percentages, parts and ratios are based on the total weight of theshampoo compositions of the present invention, unless otherwisespecified. All such weights as they pertain to listed ingredients arebased on the active level and, therefore, do not include carriers orby-products that may be included in commercially available materials,unless otherwise specified.

The styling shampoo compositions of the present invention, including theessential and some optional components thereof, are described in detailhereinafter.

Anionic Detersive Surfactant Component

The styling shampoo compositions of the present invention comprise ananionic detersive surfactant component to provide cleaning performanceto the composition. The anionic detersive surfactant component in turncomprises anionic detersive surfactant, zwitterionic or amphotericdetersive surfactant which has an attached group that is anionic at thepH of the composition, or a combination thereof. Such surfactants shouldbe physically and chemically compatible with the essential componentsdescribed herein, or should not otherwise unduly impair productstability, aesthetics or performance.

Suitable anionic detersive surfactant components for use in the shampoocomposition herein include those which are known for use in hair care orother personal care cleansing compositions. The concentration of theanionic surfactant component in the shampoo composition should besufficient to provide the desired cleaning and lather performance, andgenerally range from about 5% to about 50%, preferably from about 8% toabout 30%, more preferably from about 10% to about 25%, even morepreferably from about 12% to about 22%, by weight of the composition.

Preferred anionic surfactants suitable for use in the shampoocompositions are the alkyl and alkyl ether sulfates. These materialshave the respective formulae ROSO₃M and RO(C₂H₄O)_(x)SO₃M, wherein R isalkyl or alkenyl of from about 8 to about 18 carbon atoms, x is aninteger having a value of from 1 to 10, and M is a cation such asammonium, alkanolamines, such as triethanolamine, monovalent metals,such as sodium and potassium, and polyvalent metal cations, such asmagnesium, and calcium. Solubility of the surfactant will depend uponthe particular anionic detersive surfactants and cations chosen.

Preferably, R has from about 8 to about 18 carbon atoms, more preferablyfrom about 10 to about 16 carbon atoms, even more preferably from about12 to about 14 carbon atoms, in both the alkyl and alkyl ether sulfates.The alkyl ether sulfates are typically made as condensation products ofethylene oxide and monohydric alcohols having from about 8 to about 24carbon atoms. The alcohols can be synthetic or they can be derived fromfats, e.g., coconut oil, palm kernel oil, tallow. Lauryl alcohol andstraight chain alcohols derived from coconut oil or palm kernel oil arepreferred. Such alcohols are reacted with between about 0 and about 10,preferably from about 2 to about 5, more preferably about 3, molarproportions of ethylene oxide, and the resulting mixture of molecularspecies having, for example, an average of 3 moles of ethylene oxide permole of alcohol, is sulfated and neutralized.

Specific non limiting examples of alkyl ether sulfates which may be usedin the shampoo compositions of the present invention include sodium andammonium salts of coconut alkyl triethylene glycol ether sulfate, tallowalkyl triethylene glycol ether sulfate, and tallow alkylhexa-oxyethylene sulfate. Highly preferred alkyl ether sulfates arethose comprising a mixture of individual compounds, wherein thecompounds in the mixture have an average alkyl chain length of fromabout 10 to about 16 carbon atoms and an average degree of ethoxylationof from about 1 to about 4 moles of ethylene oxide.

Other suitable anionic detersive surfactants are the water-soluble saltsof organic, sulfuric acid reaction products conforming to the formula[R¹—SO₃—M] where R¹ is a straight or branched chain, saturated,aliphatic hydrocarbon radical having from about 8 to about 24,preferably about 10 to about 18, carbon atoms; and M is a cationdescribed hereinbefore. Non limiting examples of such detersivesurfactants are the salts of an organic sulfuric acid reaction productof a hydrocarbon of the methane series, including iso-, neo-, andn-paraffins, having from about 8 to about 24 carbon atoms, preferablyabout 12 to about 18 carbon atoms and a sulfonating agent, e.g., SO₃,H₂SO₄, obtained according to known sulfonation methods, includingbleaching and hydrolysis. Preferred are alkali metal and ammoniumsulfonated C₁₀ to C₁₈ n-paraffins.

Still other suitable anionic detersive surfactants are the reactionproducts of fatty acids esterified with isethionic acid and neutralizedwith sodium hydroxide where, for example, the fatty acids are derivedfrom coconut oil or palm kernel oil; sodium or potassium salts of fattyacid amides of methyl tauride in which the fatty acids, for example, arederived from coconut oil or palm kernel oil. Other similar anionicsurfactants are described in U.S. Pat. No. 2,486,921; U.S. Pat. No.2,486,922; and U.S. Pat. No. 2,396,278, which descriptions areincorporated herein by reference.

Other anionic detersive surfactants suitable for use in the shampoocompositions are the succinnates, examples of which include disodiumN-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammoniumlauryl sulfosuccinate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinnate; diamyl ester ofsodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid;and dioctyl esters of sodium sulfosuccinic acid.

Other suitable anionic detersive surfactants include olefin sulfonateshaving about 10 to about 24 carbon atoms. In this context, the term“olefin sulfonates” refers to compounds which can be produced by thesulfonation of alpha-olefins by means of uncomplexed sulfur trioxide,followed by neutralization of the acid reaction mixture in conditionssuch that any sulfones which have been formed in the reaction arehydrolyzed to give the corresponding hydroxy-alkanesulfonates. Thesulfur trioxide can be liquid or gaseous, and is usually, but notnecessarily, diluted by inert diluents, for example by liquid SO₂,chlorinated hydrocarbons, etc., when used in the liquid form, or by air,nitrogen, gaseous SO₂, etc., when used in the gaseous form. Thealpha-olefins from which the olefin sulfonates are derived aremono-olefins having from about 10 to about 24 carbon atoms, preferablyfrom about 12 to about 16 carbon atoms. Preferably, they are straightchain olefins. In addition to the true alkene sulfonates and aproportion of hydroxy-alkanesulfonates, the olefin sulfonates cancontain minor amounts of other materials, such as alkene disulfonatesdepending upon the reaction conditions, proportion of reactants, thenature of the starting olefins and impurities in the olefin stock andside reactions during the sulfonation process. A non limiting example ofsuch an alpha-olefin sulfonate mixture is described in U.S. Pat. No.3,332,880, which description is incorporated herein by reference.Another class of anionic detersive surfactants suitable for use in theshampoo compositions are the beta-alkyloxy alkane sulfonates. Thesesurfactants conform to the formula

where R¹ is a straight chain alkyl group having from about 6 to about 20carbon atoms, R² is a lower alkyl group having from about I to about 3carbon atoms, preferably I carbon atom, and M is a water-soluble cationas described hereinbefore.

Preferred anionic detersive surfactants for use in the shampoocompositions include ammonium lauryl sulfate, ammonium laureth sulfate,triethylamine lauryl sulfate, triethylamine laureth sulfate,triethanolamine lauryl sulfate, triethanolamine laureth sulfate,monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate,diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauricmonoglyceride sodium sulfate, sodium lauryl sulfate, sodium laurethsulfate, potassium lauryl sulfate, potassium laureth sulfate, sodiumlauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoylsarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, odiumcocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate,potassium lauryl sulfate, triethanolamine lauryl sulfate,triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate,monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate,sodium dodecyl benzene sulfonate, and combinations thereof.

Suitable amphoteric or zwitterionic detersive surfactants for use in theshampoo composition herein include those which are known for use in haircare or other personal care cleansing composition, and which contain agroup that is anionic at the pH of the shampoo composition.Concentration of such amphoteric detersive surfactants preferably rangesfrom about 0.5% to about 20%, preferably from about 1% to about 10%, byweight of the composition. Non limiting examples of suitablezwitterionic or amphoteric surfactants are described in U.S. Pat. No.5,104,646 (Bolich Jr. et al.), U.S. Pat. No. 5,106,609 (Bolich Jr. etal.), which descriptions are incorporated herein by reference.

Amphoteric detersive surfactants suitable for use in the shampoocomposition are well known in the art, and include those surfactantsbroadly described as derivatives of aliphatic secondary and tertiaryamines in which the aliphatic radical can be straight or branched chainand wherein one of the aliphatic substituents contains from about 8 toabout 18 carbon atoms and one contains an anionic water solubilizinggroup such as carboxy, sulfonate, sulfate, phosphate, or phosphonate.Preferred amphoteric detersive surfactants for use in the presentinvention include cocoamphoacetate, cocoamphodiacetate,lauroamphoacetate, lauroamphodiacetate, and mixtures thereof.

Zwitterionic detersive surfactants suitable for use in the shampoocomposition are well known in the art, and include those surfactantsbroadly described as derivatives of aliphatic quaternary ammonium,phosphonium, and sulfonium compounds, in which the aliphatic radicalscan be straight or branched chain, and wherein one of the aliphaticsubstituents contains from about 8 to about 18 carbon atoms and onecontains an anionic group such as carboxy, sulfonate, sulfate, phosphateor phosphonate. Zwitterionics such as betaines are preferred.

The shampoo compositions of the present invention may further compriseadditional surfactants for use in combination with the anionic detersivesurfactant component described hereinbefore. Suitable optionalsurfactants include nonionic surfactants. Any such surfactant known inthe art for use in hair or personal care products may be used, providedthat the optional additional surfactant is also chemically andphysically compatible with the essential components of the shampoocomposition, or does not otherwise unduly impair product performance,aesthetics or stability. The concentration of the optional additionalsurfactants in the shampoo composition may vary with the cleansing orlather performance desired, the optional surfactant selected, thedesired product concentration, the presence of other components in thecomposition, and other factors well known in the art.

Non limiting examples of other anionic, zwitterionic, amphoteric oroptional additional surfactants suitable for use in the shampoocompositions are described in McCutcheon's, Emulsifiers and Detergents,1989 Annual, published by M. C. Publishing Co., and U.S. Pat. No.3,929,678, U.S. Pat. No. 2,658,072; U.S. Pat. No. 2,438,091; U.S. Pat.No. 2,528,378, which descriptions are incorporated herein by reference.

Cationic Deposition Polymer

The shampoo compositions of the present invention comprise an organiccationic polymer as a deposition aid for the styling polymer componentdescribed hereinafter. The concentration of the cationic polymer in theshampoo composition ranges from about 0.025% to about 3%, preferablyfrom about 0.05% to about 2%, more preferably from about 0.1% to about1%, by weight of the shampoo composition.

The cationic polymer for use in the shampoo composition of the presentinvention contains cationic nitrogen-containing moieties such asquaternary ammonium or cationic protonated amino moieties. The cationicprotonated amines can be primary, secondary, or tertiary amines(preferably secondary or tertiary), depending upon the particularspecies and the selected pH of the styling shampoo composition. Theaverage molecular weight of the cationic polymer is between about 10million and about 5,000, preferably at least about 100,000, morepreferably at least about 200,000, but preferably not more than about 2million, more preferably not more than about 1.5 million. The polymersalso have a cationic charge density ranging from about 0.2 meq/gm toabout 7 meq/gm, preferably at least about 0.4 meq/gm, more preferably atleast about 0.6 meq/gm, but also preferably less than about 5 meq/gm,more preferably less than about 2 meq/gm, at the pH of intended use ofthe shampoo composition, which pH will generally range from about pH 3to about pH 9, preferably between about pH 4 and about pH 7.

Any anionic counterions can be use in association with the cationicpolymers so long as the polymers remain soluble in water, in the shampoocomposition, or in a coacervate phase of the shampoo composition, and solong as the counterions are physically and chemically compatible withthe essential components of the shampoo composition or do not otherwiseunduly impair product performance, stability or aesthetics. Non limitingexamples of such counterions include halides (e.g., chlorine, fluorine,bromine, iodine), sulfate and methylsulfate.

The cationic nitrogen-containing moiety of the cationic polymer isgenerally present as a substituent on all, or more typically on some, ofthe monomer units thereof. Thus, the cationic polymer for use in theshampoo composition includes homopolymers, copolymers, terpolymers, andso forth, of quaternary ammonium or cationic amine-substituted monomerunits, optionally in combination with non-cationic monomers referred toherein as spacer monomers. Non limiting examples of such polymers aredescribed in the CTFA Cosmetic Ingredient Dictionary, 3rd edition,edited by Estrin, Crosley, and Haynes, (The Cosmetic, Toiletry, andFragrance Association, Inc., Washington, D.C. (1982)), which descriptionis incorporated herein by reference.

Non limiting examples of suitable cationic polymers include copolymersof vinyl monomers having cationic protonated amine or quaternaryammonium functionalities with water soluble spacer monomers such asacrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl anddialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinylcaprolactone or vinyl pyrrolidone. The alkyl and dialkyl substitutedmonomers preferably have from C₁ to C₇ alkyl groups, more preferablyfrom C₁ to C₃ alkyl groups. Other suitable spacer monomers include vinylesters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), maleicanhydride, propylene glycol, and ethylene glycol.

Suitable cationic protonated amino and quaternary ammonium monomers, forinclusion in the cationic polymers of the shampoo composition herein,include vinyl compounds substituted with dialkylaminoalkyl acrylate,dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate,monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammoniumsalt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammoniumsalts, and vinyl quaternary ammonium monomers having cyclic cationicnitrogen-containing rings such as pyridinium, imidazolium, andquaternized pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl vinylpyridinium, alkyl vinyl pyrrolidone salts. The alkyl portions of thesemonomers are preferably lower alkyls such as the C₁, C₂ or C₃ alkyls.

Suitable amine-substituted vinyl monomers for use herein includedialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate,dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide,wherein the alkyl groups are preferably C₁-C₇ hydrocarbyls, morepreferably C₁-C₃, alkyls.

Other suitable cationic polymers for use in the shampoo compositioninclude copolymers of 1-vinyl-2-pyrrolidone and1-vinyl-3-methylimidazolium salt (e.g., chloride salt) (referred to inthe industry by the Cosmetic, Toiletry, and Fragrance Association,“CTFA”, as Polyquaternium-16), such as those commercially available fromBASF Wyandotte Corp. (Parsippany, N.J., U.S.A.) under the LUVIQUATtradename (e.g., LUVIQUAT FC 370); copolymers of 1-vinyl-2-pyrrolidoneand dimethylaminoethyl methacrylate (referred to in the industry by CTFAas Polyquatemium-11) such as those commercially available from ISPCorporation (Wayne, N.J., U.S.A.) under the GAFQUAT tradename (e.g.,GAFQUAT 755N); cationic diallyl quaternary ammonium-containing polymers,including, for example, dimethyldiallylammonium chloride homopolymer andcopolymers of acrylamide and dimethyldiallylammonium chloride, referredto in the industry (CTFA) as Polyquaternium 6 and Polyquatemium 7,respectively; and mineral acid salts of amino-alkyl esters ofhomopolymers and copolymers of unsaturated carboxylic acids having from3 to 5 carbon atoms, as described in U.S. Pat. No. 4,009,256, whichdescription is incorporated herein by reference.

Other suitable cationic polymers for use in the shampoo compositioninclude polysaccharide polymers, such as cationic cellulose derivativesand cationic starch derivatives. Suitable cationic polysaccharidepolymers include those which conform to the formula

wherein A is an anhydroglucose residual group, such as a starch orcellulose anhydroglucose residual; R is an alkylene oxyalkylene,polyoxyalkylene, or hydroxyalkylene group, or combination thereof, R1,R2, and R3 independently are alkyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18carbon atoms, and the total number of carbon atoms for each cationicmoiety (i.e., the sum of carbon atoms in RI, R2 and R3) preferably beingabout 20 or less; and X is an anionic counterion as described inhereinbefore.

Preferred cationic cellulose polymers are those polymers available fromAmerchol Corp. (Edison, N.J., USA) in their Polymer JR and LR series ofpolymers, as salts of hydroxyethyl cellulose reacted with trimethylammonium substituted epoxide, referred to in the industry (CTFA) asPolyquatemium 10. Another type of preferred cationic cellulose includesthe polymeric quaternary ammonium salts of hydroxyethyl cellulosereacted with lauryl dimethyl ammonium-substituted epoxide, referred toin the industry (CTFA) as Polyquaternium 24. These materials areavailable from Amerchol Corp. (Edison, NJ, USA) under the trade namePolymer LM-200.

Other suitable cationic polymers include cationic guar gum derivatives,such as guar hydroxypropyltrimonium chloride, specific examples of whichinclude the Jaguar series commercially available from Rhone-PoulencIncorporated. Other suitable cationic polymers include quaternarynitrogen-containing cellulose ethers, some examples of which aredescribed in U.S. Pat. No. 3,962,418, which description is incorporatedherein by reference herein. Other suitable cationic polymers includecopolymers of etherified cellulose, guar and starch, some examples ofwhich are described in U.S. Pat. No. 3,958,581, which description isincorporated herein by reference.

The cationic polymers herein are either soluble in the shampoocomposition, or preferably are soluble in a complex coacervate phase inthe shampoo composition formed by the cationic polymer and the anionicdetersive surfactant component described hereinbefore. Complexcoacervates of the cationic polymer can also be formed with othercharged materials in the shampoo composition.

Coacervate formation is dependent upon a variety of criteria such asmolecular weight, component concentration, and ratio of interactingionic components, ionic strength (including modification of ionicstrength, for example, by addition of salts), charge density of thecationic and anionic components, pH, and temperature. Coacervate systemsand the effect of these parameters have been described, for example, byJ. Caelles, et al., “Anionic and Cationic Compounds in Mixed Systems”,Cosmetics & Toiletries, Vol. 106, April 1991, pp 49-54, C. J. van Oss,“Coacervation, Complex-Coacervation and Flocculation”, J. DispersionScience and Technology, Vol. 9 (5,6), 1988-89, pp 561-573, and D. J.Burgess, “Practical Analysis of Complex Coacervate Systems”, J. ofColloid and Interface Science, Vol. 140, No. 1, November 1990, pp227-238, which descriptions are incorporated herein by reference.

It is believed to be particularly advantageous for the cationic polymerto be present in the shampoo composition in a coacervate phase, or toform a coacervate phase upon application or rinsing of the shampoo to orfrom the hair. Complex coacervates are believed to more readily depositon the hair. Thus, in general, it is preferred that the cationic polymerexist in the shampoo composition as a coacervate phase or form acoacervate phase upon dilution. If not already a coacervate in theshampoo composition, the cationic polymer will preferably exist in acomplex coacervate form in the shampoo upon dilution with water.

Techniques for analysis of formation of complex coacervates are known inthe art. For example, microscopic analyses of the shampoo compositions,at any chosen stage of dilution, can be utilized to identify whether acoacervate phase has formed. Such coacervate phase will be identifiableas an additional emulsified phase in the composition. The use of dyescan aid in distinguishing the coacervate phase from other insolublephases dispersed in the shampoo composition.

Styling Polymer

The shampoo compositions of the present invention comprise awater-insoluble hair styling polymer, concentrations of which range fromabout 0.1% to about 10%, preferably from about 0.3% to about 7%, morepreferably from about 0.5% to about 5%, by weight of the composition.These styling polymers provide the shampoo composition of the presentinvention with hair styling performance by providing a thin polymericfilm on the hair after application from a shampoo composition. Thepolymeric film deposited on the hair has adhesive and cohesive strength,as is understood by those skilled in the art.

Many such polymers are known in the art, including water-insolubleorganic polymers and water-insoluble silicone-grafted polymers, all ofwhich are suitable for use in the shampoo composition herein providedthat they also have the requisite features or characteristics describedhereinafter. Such polymers can be made by conventional or otherwiseknown polymerization techniques well known in the art, an example ofwhich includes free radical polymerization.

Examples of suitable organic and silicone grafted polymers for use inthe shampoo composition of the present invention are described ingreater detail hereinafter.

I. Organic Styling Polymer

The hair styling polymers suitable for use in the shampoo composition ofthe present invention include organic hair styling polymers well knownin the art. The organic styling polymers may be homopolymers,copolymers, terpolymers or other higher polymers, but must comprise oneor more polymerizable hydrophobic monomers to thus render the resultingstyling polymer hydrophobic and water-insoluble as defined herein. Thestyling polymers may therefore further comprise other water soluble,hydrophillic monomers provided that the resulting styling polymers havethe requisite hydrophobicity and water insolubility.

As used herein, the term “hydrophobic monomer” refers to polymerizableorganic monomers that can form with like monomers a water-insolublehomopolymer, and the term “hydrophilic monomer” refers to polymerizableorganic monomers that can form with like monomers a water-solublehomopolymer.

The organic styling polymers preferably have a weight average molecularweight of at least about 20,000, preferably greater than about 25,000,more preferably greater than about 30,000, most preferably greater thanabout 35,000. There is no upper limit for molecular weight except thatwhich limits applicability of the invention for practical reasons, suchas processing, aesthetic characteristics, formulateability, etc. Ingeneral, the weight average molecular weight will be less than about10,000,000, more generally less than about 5,000,000, and typically lessthan about 2,000,000. Preferably, the weight average molecular weightwill be between about 20,000 and about 2,000,000, more preferablybetween about 30,000 and about 1,000,000, and most preferably betweenabout 40,000 and about 500,000.

The organic styling polymers also preferably have a glass transitiontemperature (Tg) or crystalline melting point (Tm) of at least about−20° C., preferably from about 20° C. to about 80° C., more preferablyfrom about 20° C. to about 60° C. Styling polymers having these Tg or Tmvalues form styling films on hair that are not unduly sticky or tacky tothe touch. As used herein, the abbreviation “Tg” refers to the glasstransition temperature of the backbone of the polymer, and theabbreviation “Tm” refers to the crystalline melting point of thebackbone, if such a transition exists for a given polymer. Preferably,both the Tg and the Tm, if any, are within the ranges recitedhereinabove.

The organic styling polymers are carbon chains derived frompolymerization of hydrophobic monomers such as ethylenically unsaturatedmonomers, cellulosic chains or other carbohydrate-derived polymericchains. The backbone may comprise ether groups, ester groups, amidegroups, urethanes, combinations thereof, and the like.

The organic styling polymers may further comprise one or morehydrophilic monomers in combination with the hydrophobic monomersdescribed herein, provided that the resulting styling polymer has therequisite hydrophobic character and water-insolubility. Suitablehydrophilic monomers include, but are not limited to, acrylic acid,methacrylic acid, N,N-dimethylacrylamide, dimethyl aminoethylmethacrylate, quaternized dimethylaminoethyl methacrylate,methacrylamide, N-t-butyl acrylamide, maleic acid, maleic anhydride andits half esters, crotonic acid, itaconic acid, acrylamide, acrylatealcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride,vinyl pyrrolidone, vinyl ethers (such as methyl vinyl ether),maleimides, vinyl pyridine, vinyl imidazole, other polar vinylheterocyclics, styrene sulfonate, allyl alcohol, vinyl alcohol (such asthat produced by the hydrolysis of vinyl acetate after polymerization),salts of any acids and amines listed above, and mixtures thereof.Preferred hydrophillic monomers include acrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinyl pyrrolidone, salts of acids and amineslisted above, and combinations thereof.

Suitable hydrophobic monomers for use in the organic styling polymerinclude, but are not limited to, acrylic or methacrylic acid esters ofC₁-C₁₈ alcohols, such as methanol, ethanol, methoxy ethanol, 1-propanol,2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol,3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol,1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol,t-butanol(2-methyl-2-propanol), cyclohexanol, neodecanol,2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol,6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol,3,5,5-tri methyl-1-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol,1-octa decanol, and the like, the alcohols having from about 1 to about18 carbon atoms, preferably from about 1 to about 12 carbon atoms;styrene; polystyrene macromer; vinyl acetate; vinyl chloride; vinylidenechloride; vinyl propionate; alpha-methylstyrene; t-butylstyrene;butadiene; cyclohexadiene; ethylene; propylene; vinyl toluene; andmixtures thereof. Preferred hydrophobic monomers include n-butylmethacrylate, isobutyl methacrylate, t-butyl acrylate, t-butylmethacrylate, 2-ethythexyl methacrylate, methyl methacrylate, vinylacetate, and mixtures thereof, more preferably t-butyl acrylate, t-butylmethacrylate, or combinations thereof.

The styling polymers for use in the shampoo composition preferablycomprise from about 20% to 100%, more preferably from about 50% to about100%, even more preferably from about 60% to about 100%, by weight ofthe hydrophobic monomers, and may further comprise from zero to about80% by weight of hydrophilic monomers. The particular selection andcombination of monomers for incorporation into the styling polymer willhelp determine its formulational properties. By appropriate selectionand combination of, for example, hydrophilic and hydrophobic monomers,the styling polymer can be optimized for physical and chemicalcompatibility with the selected styling polymer solvent describedhereinafter and other components of the shampoo composition. Theselected monomer composition of the organic styling polymer must,however, render the styling polymer water-insoluble but soluble in theselected styling polymer solvent described hereinafter. In this context,the organic styling polymer is soluble in the styling polymer solvent ifthe organic polymer is solubilized in the solvent at 25° C. at thepolymer and solvent concentrations of the shampoo formulation selected.However, a solution of the organic styling polymer and styling polymersolvent may be heated to speed up solubility of the styling polymer inthe styling polymer solvent. Such styling polymer and solventformulation, including the selection of monomers for use in the stylingpolymer, to achieve the desired solubility is well within the skill ofone in the art.

Examples of preferred organic styling polymers include t-butylacrylate/2-ethylhexyl acrylate copolymers having a weight/weight ratioof monomers of about 95/5, about 90/10, about 80/20, about 70/30, about60/40, and about 50/50; t-butyl acrylate/2-ethylhexyl methacrylatecopolymers having a weight/weight ratio of monomers of about 95/5, about90/10, about 80/20, about 70/30, about 60/40, and about 50/50; t-butylmethacrylate/2-ethylhexyl acrylate copolymers having a weight/weightratio of monomers of about 95/5, about 90/10, about 80/20, about 70/30,about 60/40, and about 50/50; t-butyl methacrylate/2-ethylhexylmethacrylate copolymers having a weight/weight ratio of monomers ofabout 95/5, about 90/10, about 80/20, about 70/30, about 60/40, andabout 50/50; t-butyl ethacrylate/2-ethylhexyl methacrylate copolymershaving a weight/weight ratio of monomers of about 95/5, about 90/10,about 80/20, about 70/30, about 60/40, and about 50/50; vinylpyrrolidone/vinyl acetate copolymers having a weight/weight ratio ofmonomers of about 10/90, and about 5/95; and mixtures thereof.

Especially preferred polymers are t-butyl acrylate/2-ethylhexylmethacrylate copolymers having a weight/weight ratio of monomers ofabout 95/5, about 90/10, about 80/20, about 70/30, about 60/40, andabout 50/50; t-butyl methacrylate/2-ethylhexyl methacrylate copolymershaving a weight/weight ratio of monomers of about 95/5, about 90/10,about 80/20, about 70/30, about 60/40, and about 50/50; and mixturesthereof.

Examples of other suitable styling polymers are described in U.S. Pat.No. 5,120,531, to Wells et al., issued Jun. 9, 1992; U.S. Pat. No.5,120,532, to Wells et al., issued Jun. 9, 1992; U.S. Pat. No.5,104,642, to Wells et al., issued Apr. 14, 1992; U.S. Pat. No.4,272,511, to Papantoniou et al., issued Jun. 9, 1981; and U.S. Pat. No.4,196,190, to Gehman et al., issued Apr. 1, 1980, which descriptions areincorporated herein by reference.

II. Silicone-grafted Styling Polymer

Other suitable styling polymers for use in the shampoo composition ofthe present invention are silicone-grafted hair styling resins. Thesepolymers may be used alone or in combination with the organic stylingpolymers described hereinbefore. Many such polymers suitable for use inthe shampoo composition herein are known in the art. These polymers arecharacterized by polysiloxane moieties covalently bonded to and pendantfrom a polymeric carbon-based backbone.

The backbone of the silicone-grafted polymer is preferably a carbonchain derived from polymerization of ethylenically unsaturated monomers,but can also be cellulosic chains or other carbohydrate-derivedpolymeric chains to which polysiloxane moieties are pendant. Thebackbone can also include ether groups, ester groups, amide groups,urethane groups and the like. The polysiloxane moieties can besubstituted on the polymer or can be made by co-polymerization ofpolysiloxane-containing polymerizable monomers (e.g. ethylenicallyunsaturated monomers, ethers, and/or epoxides) withnon-polysiloxane-containing polymerizable monomers.

The silicone-grafted styling polymers for use in the shampoo compositioncomprise “silicone-containing” (or “polysiloxane-containing”) monomers,which form the silicone macromer pendant from the backbone, andnon-silicone-containing monomers, which form the organic backbone of thepolymer.

Preferred silicone-grafted polymers comprise an organic backbone,preferably a carbon backbone derived from ethylenically unsaturatedmonomers, such as a vinyl polymeric backbone, and a polysiloxanemacromer (especially preferred are polydialkylsiloxane, most preferablypolydimethylsiloxane) grafted to the backbone. The polysiloxane macromershould have a weight average molecular weight of at least about 500,preferably from about 1,000 to about 100,000, more preferably from about2,000 to about 50,000, most preferably about 5,000 to about 20,000.Organic backbones contemplated include those that are derived frompolymerizable, ethylenically unsaturated monomers, including vinylmonomers, and other condensation monomers (e.g., those that polymerizeto form polyamides and polyesters), ring-opening monomers (e.g., ethyloxazoline and caprolactone), etc. Also contemplated are backbones basedon cellulosic chains, ether-containing backbones, etc.

Preferred silicone grafted polymers for use in the shampoo compositioncomprise monomer units derived from: at least one free radicallypolymerizable ethylenically unsaturated monomer or monomers and at leastone free radically polymerizable polysiloxane-containing ethylenicallyunsaturated monomer or monomers.

The silicone grafted polymers suitable for use in the shampoocomposition generally comprise from about 1% to about 50%, by weight, ofpolysiloxane-containing monomer units and from about 50% to about 99% byweight, of non-polysiloxane-containing monomers. Thenon-polysiloxane-containing monomer units can be derived from thehydrophilic and/or hydrophobic monomer units described hereinbefore.

The styling polymer for use in the shampoo composition can thereforecomprise combinations of the hydrophobic and/or polysiloxane-containingmonomer units described herein, with or without hydrophilic comonomersas described herein, provided that the resulting styling polymer has therequisite characteristics as described herein.

Suitable polymerizable polysiloxane-containing monomers include, but arenot limited to, those monomers that conform to the formula:

X(Y)_(n)Si(R)_(3-m)Z_(m)

wherein X is an ethylenically unsaturated group copolymerizable with thehydrophobic monomers described herein, such as a vinyl group; Y is adivalent linking group; R is a hydrogen, hydroxyl, lower alkyl (e.g.C₁-C₄), aryl, alkaryl, alkoxy, or alkylamino; Z is a monovalent siloxanepolymeric moiety having a number average molecular weight of at leastabout 500, which is essentially unreactive under copolymerizationconditions, and is pendant from the vinyl polymeric backbone describedabove; n is 0 or 1; and m is an integer from 1 to 3. These polymerizablepolysiloxane-containing monomers have a weight average molecular weightas described above.

A preferred polysiloxane-containing monomer conforms to the formula:

wherein m is 1, 2 or 3 (preferably m=1); p is 0 or 1; q is an integerfrom 2 to 6; R¹ is hydrogen, hydroxyl, lower alkyl, alkoxy, alkylamino,aryl, or alkaryl (preferably R¹ is alkyl); X conforms to the formula

wherein R² is hydrogen or —COOH (preferably R² is hydrogen); R³ ishydrogen, methyl or —CH₂COOH (preferably R³ is methyl); Z conforms tothe formula:

wherein R⁴, R⁵, and R⁶ independently are lower alkyl, alkoxy,alkylamino, aryl, arylalkyl, hydrogen or hydroxyl (preferably R⁴, R⁵,and R⁶ are alkyls); and r is an integer of about 5 or higher, preferablyabout 10 to about 1500 (most preferably r is from about 100 to about250). Most preferably, R⁴, R⁵, and R⁶ are methyl, p=0, and q=3.

Another preferred polysiloxane monomer conforms to either of thefollowing formulas

or

X—CH2—(CH₂)_(S)—Si(R¹)_(3-m)—Z_(m)

wherein: s is an integer from 0 to about 6, preferably 0, 1, or 2, morepreferably 0 or 1; m is an integer from 1 to 3, preferably 1; R² isC1-C10 alkyl or C7-C10 alkylaryl, preferably C1-C6 alkyl or C7-C10alkylaryl, more preferably C1-C2 alkyl; n is an integer from 0 to 4,preferably 0 or 1, more preferably 0.

The silicone grafted styling polymers suitable for use in the shampoocomposition preferably comprise from about 50% to about 99%, morepreferably from about 60% to about 98%, most preferably from about 75%to about 95%, by weight of the polymer, of non-siliconemacromer-containing monomer units, e.g. the total hydrophobic andhydrophilic monomer units described herein, and from about 1% to about50%, preferably from about 2% to about 40%, more preferably from about5% to about 25%, of silicone macromer-containing monomer units, e.g. thepolysiloxane-containing monomer units described herein. The level ofhydrophilic monomer units can be from about 0% to about 70%, preferablyfrom about 0% to about 50%, more preferably from about 0% to about 30%,most preferably from about 0% to about 15%; the level of hydrophobicmonomer units, can be from 30% to about 99%, preferably from about 50%to about 98%, more preferably from about 70% to about 95%, mostpreferably from about 85% to about 95%.

Examples of some suitable silicone grafted polymers for use in theshampoo composition herein are listed below. Each listed polymer isfollowed by its monomer composition as weight part of monomer used inthe synthesis:

(i) t-butylacrylatye/t-butyl-methacrylate/2-ethylhexyl-methacrylate/PDMSmacromer-20,000 molecular weight macromer 31/27/32/10

(ii) t-butylmethacrylate/2-ethylhexyl-methacrylate/PDMS macromer-15,000molecular weight macromer 75/10/15

(iii) t-butylmethacrylate/2-ethylhexyl-acrylate/PDMS macromer-10,000molecular weight macromer 65/15/20

(iv) t-butylacrylate/2-ethylhexyl-acrylate/PDMS macromer-14,000molecular weight macromer 77/11/12

(v) t-butylacrylate/2-ethylhexyl-methacrylate/PDMS macromer-13,000molecular weight macromer 81/9/10

Examples of other suitable silicone grafted polymers for use in theshampoo composition of the present invention are described in EPOApplication 90307528.1, published as EPO Application 0 408 311 A2 onJan. 11, 1991, Hayama, et al.; U.S. Pat. No. 5,061,481, issued Oct. 29,1991, Suzuki et al.; U.S. Pat. No. 5,106,609, Bolich et al., issued Apr.21, 1992; U.S. Pat. No. 5,100,658, Bolich et al., issued Mar. 31, 1992;U.S. Pat. No. 5,100,657, Ansher-Jackson, et al., issued Mar. 31, 1992;U.S. Pat. No. 5,104,646, Bolich et al., issued Apr. 14, 1992; U.S. Ser.No. 07/758,319, Bolich et al, filed Aug. 27, 1991, U.S. Ser. No.07/758,320, Torgerson et al., filed Aug. 27, 1991, which descriptionsare incorporated herein by reference.

Solvent

The shampoo composition of the present invention comprises a volatilesolvent for solubilizing the hair styling polymers describedhereinbefore. The solvent helps disperse the hair styling polymer aswater-insoluble fluid particles throughout the shampoo composition,wherein the dispersed particles comprise the styling polymer and thevolatile solvent. Solvents suitable for this purpose includehydrocarbons, ethers, esters, amines, alkyl alcohols, volatile siliconederivatives and combinations thereof, many examples of which are wellknown in the art.

The volatile solvent must be water-insoluble or have a low watersolubility. The selected styling polymer, however, must also besufficiently soluble in the selected solvent to allow dispersion of thehair styling polymer and solvent combination as a separate, dispersedfluid phase in the shampoo composition.

The solvent for use in the shampoo composition must also be a volatilematerial. In this context, the term volatile means that the solvent hasa boiling point of less than about 300° C., preferably from about 90° C.to about 260° C., more preferably from about 100° C. to about 200° C.(at about one atmosphere of pressure).

The concentration of the volatile solvent in the shampoo compositionmust be sufficient to solubilize the hair styling polymer and disperseit as a separate fluid phase in the shampoo composition. Suchconcentrations generally range from about 0.10% to about 10%, preferablyfrom about 0.5% to about 8%, most preferably from about 1% to about 6%,by weight of the shampoo composition, wherein the weight ratio ofstyling polymer to solvent is preferably from about 10:90 to about70:30, more preferably from about 20:80 to about 65:35, even morepreferably from about 30:70 to about 60:40. If the weight ratio ofstyling polymer to solvent is too low, the lathering performance of theshampoo composition is negatively affected. If the ratio of polymer tosolvent is too high, the composition becomes too viscous and causesdifficulty in the dispersion of the styling polymer. The hair stylingagents should have an average particle diameter in the final shampooproduct of from about 0.05 to about 100 microns, preferably from about0.5 micron to about 25 microns. Particle size can be measured accordingto methods known in the art, including, for example optical microscopy.

Preferred volatile solvents for use in the shampoo composition are thehydrocarbon solvents, especially branched chain hydrocarbon solvents.The hydrocarbon solvents may be linear or branched, saturated orunsaturated, hydrocarbons having from about 8 to about 18 carbon atoms,preferably from about 10 to about 16 carbon atoms. Saturatedhydrocarbons are preferred, as are branched hydrocarbons. Nonlimitingexamples of some suitable linear hydrocarbons include decane, dodecane,decene, tridecene, and combinations thereof. Suitable branchedhydrocarbons include isoparaffins, examples of which includecommercially available isoparaffins from Exxon Chemical Company such asIsopar H and K (C₁₁-C₁₂ isoparaffins), and Isopar L (C₁₁-C₁₃isoparaffns). Preferred branched hydrocarbons are isohexadecane,isododecane, 2,5-dimethyl decane, isotetradecane, and combinationsthereof. Commercially available branched hydrocarbons include Permethyl99A and 101A (available from Preperse, Inc., South Plainfield, N.J.,USA).

Other suitable solvents include isopropanol, butyl alcohol, amylalcohol, phenyl ethanol, benzyl alcohol, phenyl propanol, ethylbutyrate, isopropyl butyrate, diethyl phthalate, diethyl malonate,diethyl succinate, dimethyl malonate, dimethyl succinate, phenyl ethyldimethyl carbinol, ethyl-6-acetoxyhexanoate, and methyl(2-pentanyl-3-oxy)cyclopentylacetate, and mixtures thereof. Preferredamong such other suitable solvents are diethyl phthalate, diethylmalonate, diethyl succinate, dimethyl malonate, dimethyl succinate,phenylethyl dimethyl carbinol, ethyl-6-acetoxyhexanoate, and mixturesthereof.

Suitable ether solvents are the di(C₅-C₇) alkyl ethers and diethers,especially the di(C₅-C₆) alkyl ethers such as isoamyl ether, dipentylether and dihexyl ether.

Other suitable solvents for use in the shampoo composition the volatilesilicon derivatives such as cyclic or linear polydialkylsiloxane, linearsiloxy compounds or silane. The number of silicon atoms in the cyclicsilicones is preferably from about 3 to about 7, more preferably about 3to about

The general formula for such silicones is:

wherein R₁ and R₂ are independently selected from C₁ to C₈ alkyl, arylor alkylaryl and wherein n=3-7. The linear polyorgano siloxanes havefrom about 2 to 7 silicon atoms and have the general formula:

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ can independently be saturatedor unsaturated C₁-C₈ alkyl, aryl, alkylaryl, hydroxyalkyl, amino alkylor alkyl siloxy.

Linear siloxy compounds have the general formula:

wherein R₁, R₂, R₃, R₄, R₅, and R₆ are independently selected fromsaturated or unsaturated C₁ to C₇ alkyl, aryl and alkyl aryl and R₇ isC₁ to C₄ alkylene.

Silane compounds have the general formula:

wherein R₁, R₂, R₃, and R₄ can independently be selected from C₁-C₈alkyl, aryl, alkylaryl, hydroxyalkyl and alkylsiloxy.

Silicones of the above type, both cyclic and linear, are offered by DowComing Corporation, Dow Corning 344, 345 and 200 fluids, Union Carbide,Silicone 7202 and Silicone 7158, and Stauffer Chemical, SWS-03314.

The linear volatile silicones generally have viscosities of less thanabout 5 centistokes at 25° C. while the cyclic materials haveviscosities less than about 10 centistokes. Examples of volatilesilicones are described in Todd and Byers, “Volatile Silicone Fluids forCosmetics”, Cosmetics and Toiletries, Vol. 91, January, 1976, pp. 27-32,and also in Silicon Compounds, pages 253-295, distributed by PetrarchChemicals, which descriptions are incorporated herein by reference.

Cationic Spreading Agent

The shampoo compositions of the present invention comprises selectcationic materials which act for use as spreading agents. The spreadingagents for use in the composition are select quaternary ammonium orprotonated amino compounds defined in greater detail hereinafter. Theseselect spreading agents are useful to improve spreadability of thewater-insoluble hair styling polymer on hair. The concentration of theselect spreading agents in the composition range from about 0.05% toabout 5%, preferably from about 0.1% to about 2%, more preferably fromabout 0.2% to about 1%, by weight of the shampoo composition.

It has been found that the select spreading agents will improvespreadability of a water-insoluble styling polymer when used in theshampoo composition of the present invention. In particular, theimproved insoluble solvent, water-insoluble styling polymer, andcationic deposition polymer, are especially effective at improvingstyling performance of the composition. The improved styling performanceresults from the improved spreading efficiency of water-insolublestyling polymer attributed to the use of the select spreading agent inthe composition onto hair. This improved spreading results in improvedstyling performance, or allows for formulation of the shampoocomposition using reduced amounts of styling polymer or cationicdeposition polymer.

The select spreading are quaternary ammonium or amino compounds having2, 3 or 4 N-radicals which are substituted or unsubstituted hydrocarbonchains having from about 12 to about 30 carbon atoms, wherein thesubstituents includes nonionic hydrophilic moieties selected fromalkoxy, polyoxalkylene, alkylamido, hydroxyalkyl, alkylester moieties,and mixtures thereof. Suitable hydrophile-containing radicals include,for example, compounds having nonionic hydrophile moieties selected fromthe group consisting of ethoxy, propoxy, polyoxyethylene,polyoxypropylene, ethylamido, propylamido, hydroxymethyl, hydroxyethyl,hydroxypropyl, methylester, ethylester, propylester, or mixturesthereof. The select spreading agents are cationic and must be positivelycharged at the pH of the shampoo compositions. Generally, the pH of theshampoo composition will be less than about 10, typically from about 3to about 9, preferably from about 4 to about 8.

Select cationic spreading agents for use in the composition includethose corresponding to the to the formula:

wherein R₁, and R₂ are independently a saturated or unsaturated,substituted or unsubstituted, linear or branched hydrocarbon chainhaving from about 12 to about 30 carbon atoms, preferably from about 18to about 22 carbon atoms, and wherein the hydrocarbon chain can containone or more hydophilic moieties selected from the alkoxy,polyoxyalkylene, alkylamido, hydroxyalkyl, alkylester, and mixturesthereof; R₃ and R₄ are independently a hydrogen, or a saturated orunsaturated, substituted or unsubstituted, linear or branchedhydrocarbon chain having from about 1 to about 30 carbon atoms, or ahydrocarbon having from about 1 to about 30 carbon atoms containing oneor more aromatic, ester, ether, amido, amino moieties present assubstitutents or as linkages in the chain, and wherein the hydrocarbonchain can contain one or more hydophilic moieties selected from thealkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, alkylester, andmixtures thereof; and X is a soluble salt forming anion preferablyselected from halogen (especially chlorine), acetate, phosphate,nitrate, sulfonate, and alkylsulfate radicals.

An example of a select spreading agent for use in the compositioninclude those corresponding to the formula:

wherein n is from 10-28, preferably 16, and X is a water soluble saltforming anion (e.g., Cl, sulfate, etc.).

Other examples of select cationic spreading agents for use in thecomposition include those corresponding to the formula:

wherein Z₁ and Z₂ are independently saturated or unsaturated,substituted or unsubstituted, linear or branched hydrocarbons, andpreferably Z₁ is an alkyl, more preferably methyl, and Z₂ is a shortchain hydroxyalkyl, preferably hydroxymethyl or hydroxyethyl; n and mare independently integers from 1 to 4, inclusive, preferably from 2 to3, inclusive, more preferably 2; R′ and R″ are independently substitutedor unsubstituted hydrocarbons, preferably C₁₂-C₂₀ alkyl or alkenyl; andX is a soluble salt forming anion (e.g., Cl, sulfate, etc.).

Nonlimiting examples of suitable cationic spreading agents includeditallowdimethyl ammonium chloride, ditallowdimethyl ammonium methylsulfate, dihexadecyl dimethyl ammonium chloride, di-(hydrogenatedtallow) dimethyl ammonium chloride, dioctadecyl dimethyl ammoniumchloride, dieicosyl dimethyl ammonium chloride, didocosyl dimethylammonium chloride, di-(hydrogenated tallow) dimethyl ammonium acetate,dihexadecyl dimethyl ammonium acetate, ditallow dipropyl ammoniumphosphate, ditallow dimethyl ammonium nitrate, di-(coconutalkyl)dimethyl ammonium chloride, ditallowamidoethyl hydroxypropylmoniummethosulfate (commercially available as Varisoft 238), dihydrogenatedtallowamidoethyl hydroxyethylmonium methosulfate (commercially availableas Varisoft 110), ditallowamidoethyl hydroxyethylmonium methosulfate(commercially available as Varisoft 222), and di(partially hardenedsoyoylethyl) hydroxyethylmonium methosulfate (commercially available asArmocare EQ-S). Ditallowdimethyl ammonium chloride, ditallowamidoethylhydroxypropylmonium methosulfate, dihydrogenated tallowamidoethylhydroxyethylmonium methosulfate, ditallowamidoethyl hydroxyethylmoniummethosulfate, and di(partially hardened soyoylethyl) hydroxyethylmoniummethosulfate are particularly preferred quaternary ammonium cationicsurfactants useful herein.

Other suitable quaternary ammonium cationic surfactants are described inM.C. Publishing Co., McCutcheion's Detergents & Emulsifiers, (NorthAmerican edition 1979); Schwartz, et al., Surface Active Agents. TheirChemistry and Technology, New York: Interscience Publishers, 1949; U.S.Pat. No. 3,155,591, to Hilfer, issued Nov. 3, 1964; U.S. Pat. No.3,929,678 to Laughlin et al., issued Dec. 30, 1975; U.S. Pat. No.3,959,461 to Bailey et al, issued May 25, 1976; and U.S. Pat. No.4,387,090 to Bolich Jr., issued Jun. 7, 1983, which descriptions areincorporated herein by reference.

Water

The shampoo compositions of the present invention are aqueous systemswhich comprise from about 22% to about 94.3%, preferably from about 55%to about 85%, more preferably from about 60% to about 75%, of water byweight of the shampoo composition.

Optional Components

The shampoo compositions of the present invention may further compriseone or more optional components known for use in hair care or personalcare products, provided that the optional components are physically andchemically compatible with the essential component described herein, ordo not otherwise unduly impair product stability, aesthetics orperformance. Individual concentrations of such optional components mayrange from about 0.001% to about 10% by weight of the shampoocompositions.

Non limiting examples of optional components for use in the shampoocomposition include anti dandruff agents, conditioning agents(hydrocarbon oils, fatty esters, silicones) dyes, nonvolatile solventsor diluents (water soluble and insoluble), pearlescent aids, foamboosters, additional surfactants or nonionic cosurfactants,pediculocides, pH adjusting agents, perfumes, preservatives, proteins,skin active agents, sunscreens, vitamins, and viscosity adjustingagents.

The shampoo composition of the present invention preferably furthercomprises a suspending or thickening agent. Suitable suspending agentsfor such materials are well known in the art, and include crystallineand polymeric suspending or thickening agents. Crystalline suspendingagents are preferred, and include known acyl derivatives and amineoxides, and are described in U.S. Pat. No. 4,741,855, which descriptionis incorporated herein by reference.

Non limiting examples of optional polymeric thickening agents for use inthe shampoo composition include carboxyvinyl polymers, cellulose ethers,guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guargum, starch and starch derivatives, and xantham gum. Suspending orthickening agents are described in U.S. Pat. No. 2,798,053, U.S. Pat.No. 4,686,254, U.S. Pat. No. 4,788,006, and U.S. Pat. No. 5,275,761,which descriptions are incorporated herein by reference. The optionalsuspending or thickening agents are described in more detailhereinafter. The shampoo compositions of the present invention alsopreferably comprises a silicone hair conditioning agent, more preferablya silicone hair conditioning agent in combination with an optionalsuspending agent for the silicone. The silicone hair conditioning agentis preferably non volatile, and is preferably present in the shampoocomposition at concentrations ranging from about 0.01% to about 10% byweight of the shampoo composition. Non limiting examples of suitablesilicone hair conditioning agents, and optional suspending agents forthe silicone, are described in U.S. Reissue Pate. No. 34,584 (Grote etal.), U.S. Pat. No. 5,104,646 (Bolich Jr. et al.), U.S. Pat. No.5,106,609 (Bolich Jr. et al.), which descriptions are incorporatedherein by reference. The optional silicone hair conditioning agent, andoptional suspending agents for the optional silicone, are described inmore detail hereinafter

Optional Silicone Hair Conditioning Agent

The shampoo compositions of the present invention may further comprisean optional silicone hair conditioning agent at concentrations effectiveto provide hair conditioning benefits. Such concentrations range fromabout 0.01% to about 10%, preferably from about 0.1% to about 8%, morepreferably from about 0.1% to about 5%, most preferably from about 0.2%to about 3%, by weight of the shampoo compositions.

The optional silicone hair conditioning agents are insoluble in theshampoo compositions, and are preferably nonvolatile. Typically it willbe intermixed in the shampoo composition so as to be in the form of aseparate, discontinuous phase of dispersed, insoluble particles, alsoreferred to as droplets. These droplets are typically suspended with anoptional suspending agent described hereinafter. The optional siliconehair conditioning agent phase will comprise a silicone fluid hairconditioning agent such as a silicone fluid and can also comprise otheringredients, such as a silicone resin to improve silicone fluiddeposition efficiency or enhance glossiness of the hair (especially whenhigh refractive index (e.g. above about 1.46) silicone conditioningagents are used (e.g. highly phenylated silicones).

The optional silicone hair conditioning agent phase may comprisevolatile silicone, nonvolatile silicone, or combinations thereof.Typically, if volatile silicones are present, it will be incidental totheir use as a solvent or carrier for commercially available forms ofnonvolatile silicone materials ingredients, such as silicone gums andresins.

The optional silicone hair conditioning agents for use in the shampoocompositions preferably have a viscosity of from about 20 to about2,000,000 centistokes, more preferably from about 1,000 to about1,800,000 centistokes, even more preferably from about 50,000 to about1,500,000 centistokes, most preferably from about 100,000 to about1,500,000 centistokes, as measured at 25° C.

Optional silicone fluids include silicone oils which are flowablesilicone materials having a a viscosity of less than 1,000,000centistokes, preferably between about 5 and 1,000,000 centistokes, morepreferably between about 10 and about 100,000 centistokes, at 25° C.Suitable silicone oils include polyalkyl siloxanes, polyaryl siloxanes,polyalkylaryl siloxanes, polyether siloxane copolymers, and combinationsthereof. Other insoluble, nonvolatile silicone fluids having hairconditioning properties can also be used.

Optional silicone oils include polyalkyl or polyaryl siloxanes whichconform to the following formula (I)

where R is aliphatic, preferably alkyl or alkenyl, or aryl, R can besubstituted or unsubstituted, and x is an integer from 1 to about 8,000.Suitable unsubstituted R groups include alkoxy, aryloxy, alkaryl,arylalkyl, arylalkenyl, alkylamine, and ether-substituted,hydroxyl-substituted, and halogen-substituted aliphatic and aryl groups.Suitable R groups also include cationic amines and quaternary ammoniumgroups.

The aliphatic or aryl groups substituted on the siloxane chain may haveany structure so long as the resulting silicones remain fluid at roomtemperature, are hydrophobic, are neither irritating, toxic norotherwise harmful when applied to the hair, are compatible with theother components of the shampoo compositions, are chemically stableunder normal use and storage conditions, are insoluble in the shampoocompositions herein, and are capable of being deposited on andconditioning the hair.

The two R groups on the silicon atom of each monomeric silicone unit mayrepresent the same or different groups. Preferably, the two R groupsrepresent the same group.

Preferred alkyl and alkenyl substituents are C₁-C₅ alkyls and alkenyls,more preferably from C₁-C₄, most preferably from C₁-C₂. The aliphaticportions of other alkyl-, alkenyl-, or alkynyl-containing groups (suchas alkoxy, alkaryl, and alkamino) can be straight or branched chains andpreferably have from one to five carbon atoms, more preferably from oneto four carbon atoms, even more preferably from one to three carbonatoms, most preferably from one to two carbon atoms. As discussed above,the R substituents hereof can also contain amino functionalities, e.g.alkamino groups, which can be primary, secondary or tertiary amines orquaternary ammonium. These include mono-, di- and tri- alkylamino andalkoxyamino groups wherein the aliphatic portion chain length ispreferably as described above. The R substituents can also besubstituted with other groups, such as halogens (e.g. chloride,fluoride, and bromide), halogenated aliphatic or aryl groups, andhydroxy (e.g. hydroxy substituted aliphatic groups). Suitablehalogenated R groups could include, for example, tri-halogenated(preferably fluoro) alkyl groups such as —R¹—C(F)₃, wherein R¹ is C₁-C₃alkyl. Examples of such polysiloxanes include polymethyl-3,3,3trifluoropropylsiloxane.

Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyland phenylmethyl. The preferred silicones are polydimethyl siloxane,polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxaneis especially preferred. Other suitable R groups include methyl,methoxy, ethoxy, propoxy, and aryloxy. The three R groups on the endcaps of the silicone may also represent the same or different groups.

The nonvolatile polyalkylsiloxane fluids that may be used include, forexample, polydimethylsiloxanes. These siloxanes are available, forexample, from the General Electric Company in their Viscasil R and SF 96series, and from Dow Corning in their Dow Coming 200 series.

The polyalkylaryl siloxane fluids that may be used, also include, forexample, polymethylphenylsiloxanes. These siloxanes are available, forexample, from the General Electric Company as SF 1075 methyl phenylfluid or from Dow Coming as 556 Cosmetic Grade Fluid.

The polyether siloxane copolymers that may be used include, for example,a polypropylene oxide modified polydimethylsiloxane (e.g., Dow CorningDC-1248) although ethylene oxide or mixtures of ethylene oxide andpropylene oxide may also be used. The ethylene oxide and polypropyleneoxide concentrations must be sufficiently low to prevent solubility inwater and the composition hereof.

Suitable alkylamino substituted silicones include those which conform tothe following structure (II)

wherein x and y are integers. This polymer is also known as“amodimethicone”.

Suitable cationic silicone fluids include those which conform to theformula (III)(R₁)_(a)G3-a—Si—(—OSiG₂)_(n)—(—OSiGb(R₁)_(2-b))_(m)—O—SiG3-a(R₁)_(a),wherein G is selected from the group consisting of hydrogen, phenyl,hydroxy, C₁-C₈ alkyl and preferably methyl; a is 0 or an integer havinga value from I to 3, preferably 0; b is 0 or 1, preferably 1; the sumn+m is a number from 1 to 2,000 and preferably from 50 to 150, n beingable to denote a number from 0 to 1,999 and preferably from 49 to 149and m being able to denote an integer from 1 to 2,000 and preferablyfrom 1 to 10; R₁ is a monovalent radical conforming to the formulaCqH_(2q)L in which q is an integer having a value of from 2 to 8 and Lis selected from the following groups:

—N(R₂)CH₂—CH₂—N(R₂)₂

—N(R₂)₂

—N(R₂)₃A

—N(R₂)CH₂—CH₂—NR₂H₂A

in which R₂ is selected from the group consisting of hydrogen, phenyl,benzyl, a saturated hydrocarbon radical, preferably an alkyl radicalcontaining from 1 to 20 carbon atoms, and A⁻ is a halide ion.

An especially preferred cationic silicone corresponding to formula (III)is the polymer known as “trimethylsilylamodimethicone”, of formula (IV):

Other silicone cationic polymers which can be used in the shampoocompositions are represented by the formula (V):

where R³ denotes a monovalent hydrocarbon radical having from 1 to 18carbon atoms, preferably an alkyl or alkenyl radical such as methyl; R₄denotes a hydrocarbon radical, preferably a C₁-C₁₈ alkylene radical or aC₁-C₁₈, and more preferably C₁-C₈, alkyleneoxy radical; Q is a halideion, preferably chloride; r denotes an average statistical value from 2to 20, preferably from 2 to 8; s denotes an average statistical valuefrom 20 to 200, and preferably from 20 to 50. A preferred polymer ofthis class is available from Union Carbide under the name “UCAR SILICONEALE 56.”

Other optional silicone fluids are the insoluble silicone gums. Thesegums are polyorganosiloxane materials having a viscosity at 25° C. ofgreater than or equal to 1,000,000 centistokes. Silicone gums aredescribed in U.S. Pat. No. 4,152,416; Noll and Walter, Chemistry andTechnology of Silicones, New York: Academic Press 1968; and in GeneralElectric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE76, all of which are incorporated herein by reference. The silicone gumswill typically have a mass molecular weight in excess of about 200,000,generally between about 200,000 and about 1,000,000, specific examplesof which include polydimethylsiloxane, (polydimethylsiloxane)(methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenylsiloxane)(methylvinylsiloxane) copolymer and mixtures thereof.

Another category of nonvolatile, insoluble silicone fluid conditioningagents are the high refractive index silicones, having a refractiveindex of at least about 1.46, preferably at least about 1.48, morepreferably at least about 1.52, most preferably at least about 1.55. Therefractive index of the polysiloxane fluid will generally be less thanabout 1.70, typically less than about 1.60. In this context,polysiloxane “fluid” includes oils as well as gums.

The high refractive index polysiloxane fluid includes those representedby general Formula (I) above, as well as cyclic polysiloxanes such asthose represented by Formula (VI) below:

wherein R is as defined above, n is from about 3 to about 7, preferablyfrom 3 to 5.

The high refractive index polysiloxane fluids contain a sufficientamount of aryl-containing R substituents to increase the refractiveindex to the desired level, which is described above. In addition, R andn must be selected so that the material is nonvolatile, as definedabove.

Aryl-containing substituents contain alicyclic and heterocyclic five andsix membered aryl rings, and substituents containing fused five or sixmembered rings. The aryl rings themselves can be substituted orunsubstituted. Substituents include aliphatic substituents, and can alsoinclude alkoxy substituents, acyl substituents, ketones, halogens (e.g.,Cl and Br), amines, etc. Exemplary aryl-containing groups includesubstituted and unsubstituted arenes, such as phenyl, and phenylderivatives such as phenyls with C₁-C₅ alkyl or alkenyl substituents,e.g., allylphenyl, methyl phenyl and ethyl phenyl, vinyl phenyls such asstyrenyl, and phenyl alkynes (e.g. phenyl C₂-C₄ alkynes). Heterocyclicaryl groups include substituents derived from furan, imidazole, pyrrole,pyridine, etc. Fused aryl ring substituents include, for example,napthalene, coumarin, and purine.

In general, the high refractive index polysiloxane fluids will have adegree of aryl-containing substituents of at least about 15%, preferablyat least about 20%, more preferably at least about 25%, even morepreferably at least about 35%, most preferably at least about 50%.Typically, although it is not intended to necessarily limit theinvention, the degree of aryl substitution will be less than about 90%,more generally less than about 85%, preferably from about 55% to about80%.

The polysiloxane fluids are also characterized by relatively highsurface tensions as a result of their aryl substitution. In general, thepolysiloxane fluids hereof will have a surface tension of at least about24 dynes/cm², typically at least about 27 dynes/cm². Surface tension,for purposes hereof, is measured by a de Nouy ring tensiometer accordingto Dow Corning Corporate Test Method CTM 0461, Nov. 23, 1971. Changes insurface tension can be measured according to the above test method oraccording to ASTM Method D 1331.

Preferred high refractive index polysiloxane fluids have a combinationof phenyl or phenyl derivative substituents (preferably phenyl), withalkyl substituents, preferably C₁-C₄ alkyl (most preferably methyl),hydroxy, C₁-C₄ alkylamino (especially —R¹NHR²NH² where each R¹ and R²independently is a C₁-C₃ alkyl, alkenyl, and/or alkoxy. High refractiveindex polysiloxanes are available from Dow Corning Corporation (Midland,Mich., U.S.A.) Huls America (Piscataway, N.J., U.S.A.), and GeneralElectric Silicones (Waterford, N.Y., U.S.A.).

References disclosing examples of some suitable silicone fluids for usein the shampoo compositions include U.S. Pat. No. 2,826,551, U.S. Pat.No. 3,964,500, U.S. Pat. No. 4,364,837, British Patent 849,433, andSilicon Compounds, Petrarch Systems, Inc. (1984), all of which areincorporated herein by reference.

Silicone resins can be included in the silicone conditioning agent.These resins are highly crosslinked polymeric siloxane systems. Thecrosslinking is introduced through the incorporation of trifunctionaland tetrafunctional silanes with monofunctional or difunctional, orboth, silanes during manufacture of the silicone resin. As is wellunderstood in the art, the degree of crosslinking that is required inorder to result in a silicone resin will vary according to the specificsilane units incorporated into the silicone resin. In general, siliconematerials which have a sufficient level of trifunctional andtetrafunctional siloxane monomer units (and hence, a sufficient level ofcrosslinking) such that they dry down to a rigid, or hard, film areconsidered to be silicone resins. The ratio of oxygen atoms to siliconatoms is indicative of the level of crosslinking in a particularsilicone material. Silicone materials which have at least about 1.1oxygen atoms per silicon atom will generally be silicone resins herein.Preferably, the ratio of oxygen:silicon atoms is at least about 1.2:1.0.Silanes used in the manufacture of silicone resins include monomethyl-,dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-,monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, withthe methyl-substituted silanes being most commonly utilized. Preferredresins are offered by General Electric as GE SS4230 and SS4267.Commercially available silicone resins will generally be supplied in adissolved form in a low viscosity volatile or nonvolatile siliconefluid. The silicone resins for use herein should be supplied andincorporated into the present compositions in such dissolved form, aswill be readily apparent to those skilled in the art.

Background material on silicones including sections discussing siliconefluids, gums, and resins, as well as manufacture of silicones, can befound in Encyclopedia of Polymer Science and Engineering, Volume 15,Second Edition, pp 204-308, John Wiley & Sons, Inc., 1989, incorporatedherein by reference.

Silicone materials and silicone resins in particular, can convenientlybe identified according to a shorthand nomenclature system well known tothose skilled in the art as “MDTQ” nomenclature. Under this system, thesilicone is described according to presence of various siloxane monomerunits which make up the silicone. Briefly, the symbol M denotes themonofunctional unit (CH₃)₃SiO_(0.5); D denotes the difunctional unit(CH₃)₂SiO; T denotes the trifunctional unit (CH₃)SiO₁ 5; and Q denotesthe quadri- or tetra-functional unit SiO₂. Primes of the unit symbols,e.g., M′, D′, T′, and Q′ denote substituents other than methyl, and mustbe specifically defined for each occurrence. Typical alternatesubstituents include groups such as vinyl, phenyls, amines, hydroxyls,etc. The molar ratios of the various units, either in terms ofsubscripts to the symbols indicating the total number of each type ofunit in the silicone (or an average thereof) or as specificallyindicated ratios in combination with molecular weight complete thedescription of the silicone material under the MDTQ system. Higherrelative molar amounts of T, Q, T′ and/or Q′ to D, D′, M and/or M′ in asilicone resin is indicative of higher levels of crosslinking. Asdiscussed before, however, the overall level of crosslinking can also beindicated by the oxygen to silicon ratio.

The silicone resins for use herein which are preferred are MQ, MT, MTQ,MDT and MDTQ resins. Thus, the preferred silicone substituent is methyl.Especially preferred are MQ resins wherein the M:Q ratio is from about0.5:1.0 to about 1.5:1.0 and the average molecular weight of the resinis from about 1000 to about 10,000.

The weight ratio of the nonvolatile silicone fluid, having refractiveindex below 1.46, to the silicone resin component, when used, ispreferably from about 4:1 to about 400:1, preferably this ratio is fromabout 9:1 to about 200:1, more preferably from about 19:1 to about100:1, particularly when the silicone fluid component is apolydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluidand polydimethylsiloxane gum as described above. Insofar as the siliconeresin forms a part of the same phase in the compositions hereof as thesilicone fluid, i.e. the conditioning active, the sum of the fluid andresin should be included in determining the level of siliconeconditioning agent in the composition.

Optional Suspending Agent

The shampoo compositions of the present invention may further comprise asuspending agent at concentrations effective for suspending the optionalsilicone hair conditioning agent, or other water-insoluble material, indispersed form in the shampoo compositions. Such concentrations rangefrom about 0.1% to about 10%, preferably from about 0.3% to about 5.0%,by weight of the shampoo compositions.

Optional suspending agents include crystalline suspending agents thatcan be categorized as acyl derivatives, long chain amine oxides, orcombinations thereof, concentrations of which range from about 0.1% toabout 5.0%, preferably from about 0.5% to about 3.0%, by weight of theshampoo compositions. When used in the shampoo compositions, thesesuspending agents are present in crystalline form. These suspendingagents are described in U.S. Pat. No. 4,741,855, which description isincorporated herein by reference. These preferred suspending agentsinclude ethylene glycol esters of fatty acids preferably having fromabout 16 to about 22 carbon atoms. More preferred are the ethyleneglycol stearates, both mono and distearate, but particularly thedistearate containing less than about 7% of the mono stearate. Othersuitable suspending agents include alkanol amides of fatty acids,preferably having from about 16 to about 22 carbon atoms, morepreferably about 16 to 18 carbon atoms, preferred examples of whichinclude stearic monoethanolamide, stearic diethanolamide, stearicmonoisopropanolamide and stearic monoethanolamide stearate. Other longchain acyl derivatives include long chain esters of long chain fattyacids (e.g., stearyl stearate, cetyl palmitate, etc.); glyceryl esters(e.g., glyceryl distearate) and long chain esters of long chain alkanolamides (e.g., stearamide diethanolamide distearate, stearamidemonoethanolamide stearate). Long chain acyl derivatives, ethylene glycolesters of long chain carboxylic acids, long chain amine oxides, andalkanol amides of long chain carboxylic acids in addition to thepreferred materials listed above may be used as suspending agents. Forexample, it is contemplated that suspending agents with long chainhydrocarbyls having C₈-C₂₂ chains may be used.

Other long chain acyl derivatives suitable for use as suspending agentsinclude N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof(e.g., Na, K), particularly N,N-di(hydrogenated) C₁₆, C₁₈ and tallowamido benzoic acid species of this family, which are commerciallyavailable from Stepan Company (Northfield, Ill., USA).

Examples of suitable long chain amine oxides for use as suspendingagents include alkyl (C₁₆-C₂₂) dimethyl amine oxides, e.g., stearyldimethyl amine oxide

Other suitable suspending agents include xanthan gum at concentrationsranging from about 0.3% to about 3%, preferably from about 0.4% to about1.2%, by weight of the shampoo compositions. The use of xanthan gum as asuspending agent in silicone containing shampoo compositions isdescribed, for example, in U.S. Pat. No. 4,788,006, which description isincorporated herein by reference. Combinations of long chain acylderivatives and xanthan gum may also be used as a suspending agent inthe shampoo compositions. Such combinations are described in U.S. Pat.No. 4,704,272, which description is incorporated herein by reference.

Other suitable suspending agents include carboxyvinyl polymers.Preferred among these polymers are the copolymers of acrylic acidcrosslinked with polyallylsucrose as described in U.S. Pat. No.2,798,053, which description is incorporated herein by reference.Examples of these polymers include Carbopol 934, 940, 941, and 956,available from B. F. Goodrich Company.

Other suitable suspending agents include primary amines having a fattyalkyl moiety having at least about 16 carbon atoms, examples of whichinclude palmitamine or stearamine, and secondary amines having two fattyalkyl moieties each having at least about 12 carbon atoms, examples ofwhich include dipalmitoylamine or di(hydrogenated tallow)amine. Stillother suitable suspending agents include di(hydrogenated tallow)phthalicacid amide, and crosslinked maleic anhydride-methyl vinyl ethercopolymer.

Other suitable suspending agents may be used in the shampoocompositions, including those that can impart a gel-like viscosity tothe composition, such as water soluble or colloidally water solublepolymers like cellulose ethers (e.g., methylcellulose, hydroxybutylmethylcellulose, hyroxypropylcellulose, hydroxypropyl methylcellulose,hydroxyethyl ethylcellulose and hydorxethylcellulose), guar gum,polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starchand starch derivatives, and other thickeners, viscosity modifiers,gelling agents, etc. Mixtures of these materials can also be used.

Method of Use

The shampoo compositions of the present invention are used in aconventional manner for cleansing and styling hair. An effective amountof the composition for cleansing and styling the hair is applied to thehair, that has preferably been wetted with water, and is then rinsedoff. Such effective amounts generally range from about 1 gm to about 50gm, preferably from about 1 gm to about 20 gm. Application to the hairtypically includes working the composition through the hair such thatmost or all of the hair is contacted with the composition.

This method for cleansing and styling the hair comprises the steps of a)wetting the hair with water, b) applying an effective amount of theshampoo composition to the hair, c) shampooing the hair with thecomposition, and d) rinsing the composition from the hair with water.These steps can be repeated as many times as desired to achieve thecleansing and styling benefit desired. The method is preferably employeddaily, every other day, or every third day, to provide and maintain thehair cleansing and styling performance described herein.

EXAMPLES

The styling shampoo compositions illustrated in Examples I-XV illustratespecific embodiments of the shampoo compositions of the presentinvention, but are not intended to be limiting thereof. Othermodifications can be undertaken by the skilled artisan without departingfrom the spirit and scope of this invention. These exemplifiedembodiments of the styling shampoo compositions of the present inventionprovide cleansing of hair and improved hair styling performance.

The shampoo compositions illustrated in Examples I-XV are prepared byconventional formulation and mixing methods, an example of which is setforth hereinbelow. All exemplified amounts are listed as weight percentsand exclude minor materials such as diluents, filler, and so forth,unless otherwise specified.

Preparation

The styling shampoo compositions of the present invention may beprepared using conventional formulation and mixing techniques. The hairstyling polymer should first be dissolved in the volatile solvent. Thisstyling polymer/volatile solvent premix may then be added to a premix ofthe surfactants, or some portion of the surfactants, and the solidcomponents which has been heated to melt the solid components, e.g.,about 72° C. This mixture is then pumped through a high shear mill andcooled, and then the remaining components are mixed in. Alternatively,the styling polymer/volatile solvent premix may be added to this finalmix, after cooling. The composition should have a final viscosity offrom about 2000 to about 12,000 cps. The viscosity of the compositioncan be adjusted using sodium chloride or ammonium xylenesulfonate asneeded.

The styling polymer/volatile solvent premix, as exemplified in thefollowing examples, may be a combination of styling polymers/solvent asdescribed hereinbelow.

w/w ratio Mixture A. Styling Polymer: t-butyl acrylate/2-ethylhexylmethacrylate 40 (90.10 w/w) Volatile Solvent: isododecane 60 Mixture B.Styling Polymer: t-butyl acrylate/2-ethylhexyl methacrylate 50 (90/10w/w) Volatile Solvent: isododecane 50 Mixture C. Styling Polymer:t-butyl acrylate/2-ethylhexyl 40 methacrylate/PDMS macromer (81/9/10w/w) Volatile Solvent: isododecane 60 Mixture D. Styling Polymer: vinylpyrrolidone/vinyl acetate (5/95 w/w) 40 Volatile Solvent: diethylsuccinate 60 Weight % Component I II III IV V Ammonium Laureth 2.0 2.03.0 2.0 3.0 Sulfate Cocamidopropyl Betaine 6.0 6.0 9.0 6.0 9.0 FB AlkylGlyceryl Sulfonate 10.0 10.0 6.0 10.0 6.0 Mixture A 3.0 6.0 — — —Mixture B — — 3.0 — 6.0 Mixture C — — — 3.0 — Dihydrogenated 0.25 0.50 —0.25 — Tallowamidoethyl Hydroxyethylmonium Methosulfate (1)Ditallowamidoethyl — — 0.25 — 0.25 Hydroxypropylmonium Methosulfate (2)Polyquaternium-16 — — — 0.25 — (Luviquat 905) Monosodium Phosphate 0.10.1 0.1 0.1 0.1 Disodium Phosphate 0.2 0.2 0.2 0.2 0.2 Glycol Distearate2.0 2.0 2.0 2.0 2.0 Cocomonoethanol amide 0.6 0.6 0.6 0.6 0.6 Fragrance1.0 1.0 1.0 1.0 1.0 Cetyl Alcohol 0.42 0.42 0.42 0.42 0.60 StearylAlcohol 0.18 0.18 0.18 0.18 — PEG-150 Pentaerythrityl 0.1 0.1 0.1 0.10.1 Tetrastearate Polyquaternium 10 0.3 — — 0.1 — (JR30M) Polyquaternium10 — 0.3 — — — (JR400) Polyquaternium 10 — — 0.3 — 0.1 (JR125)Dimethicone — 0.3 0.3 — — DMDM Hydantoin 0.2 0.2 0.2 0.2 0.2 Water qs100 qs 100 qs 100 qs 100 qs 100 (1) Available under the tradenameVarisoft 110 from Sherex Chemical Co. (Dublin, Ohio, USA) (2) Availableunder the tradename Varisoft 238 from Sherex Chemical Co. (Dublin, Ohio,USA)

Weight % Component VI VII VIII IX X Ammonium Lauryl 1.0 1.0 1.0 1.0 1.0Sulfate Ammonium Laureth 9.5 9.5 9.5 7.5 9.5 Sulfate Sodium 7.5 7.5 7.58.5 7.5 Lauroamphoacetate Mixture A 4.0 6.0 — — 4.0 Mixture B — — 4.0 —— Mixture C — — — 4.0 — Dihydrogenated 1.0 — — — — TallowamidoethylHydroxyethylmonium Methosulfate (1) Ditallowamidoethyl — 0.75 — — —Hydroxypropylmonium Methosulfate (2) Ditallow Dimethyl — — 1.0 — 1.0Ammonium Chloride (3) Ditallowamidoethyl — — — 0.75 — HydroxyethylmoniumMethosulfate (4) Polyquaternium-16 — — — 0.25 — (Luviquat 905)Monosodium Phosphate 0.1 0.1 0.1 0.1 0.1 Disodium Phosphate 0.2 0.2 0.20.2 0.2 Glycol Distearate 2.0 2.0 2.0 2.0 2.0 Cocomonoethanol amide 0.60.6 0.6 0.6 0.6 Fragrance 1.0 0.8 1.0 1.0 1.0 Cetyl Alcohol 0.42 0.420.42 0.42 0.42 Stearyl Alcohol 0.18 0.18 0.18 0.18 0.18 PEG-150Pentaerythrityl 0.08 0.1 0.1 0.1 0.1 Tetrastearate Polyquaternium 10 0.3— — 0.1 0.3 (JR30M) Polyquaternium 10 — 0.3 — — — (JR400) Polyquaternium10 — — 0.3 — — (JR125) Dimethicone — 0.5 0.3 — — DMDM Hydantoin 0.2 0.20.2 0.2 0.2 Water qs 100 qs 100 qs 100 qs 100 qs 100 (1) Available underthe tradename Varisoft 110 from Sherex Chemical Co. (Dublin, Ohio, USA)(2) Available under the tradename Varisoft 238 from Sherex Chemical Co.(Dublin, Ohio, USA) (3) Available under the tradename Adogen 442-110Pfrom Witco (Dublin, Ohio, USA) (4) Available under the tradenameVarisoft 222 from Sherex Chemical Co. (Dublin, Ohio, USA)

Weight % Component XI XII XIII XIV XV Ammonium Lauryl — 1.0 — 1.0 1.0Sulfate Ammonium Laureth 2.0 9.5 9.3 9.5 9.5 Sulfate CocamidopropylBetaine 6.0 — 4.7 — — FB Sodium — 7.5 — 7.5 7.5 Lauroamphoacetate AlkylGlyceryl Sulfonate 10.0 — — — — Mixture A — — — 4.0 — Mixture C — — — —4.0 Mixture D 6.0 4.0 8.0 — — Dihydrogenated 0.25 — — 0.5 —Tallowamidoethyl Hydroxyethylmonium Methosulfate (1) Ditallow Dimethyl —1.0 — — — Ammonium Chloride (3) Di(partially hardened — — 0.75 — 1.0soyoylethyl) Hydroxyethylmonium Methosulfate (5) Polyquaternium-16 — — —0.25 — (Luviquat 905) Monosodium Phosphate 0.1 0.1 0.1 0.1 0.1 DisodiumPhosphate 0.2 0.2 0.2 0.2 0.2 Glycol Distearate 2.0 2.0 2.0 2.0 2.0Cocomonoethanol amide 0.6 0.6 0.6 0.6 0.6 Fragrance 1.0 1.0 1.0 1.0 1.0Cetyl Alcohol 6.42 0.42 0.42 0.42 0.42 Stearyl Alcohol 0.18 0.18 0.180.18 0.18 PEG-150 Pentaerythrityl 0.10 0.08 1.0 0.10 0.08 TetrastearatePolyquaternium 10 — — 0.3 — — (JR30M) Polyquaternium 10 — 0.3 — — —(JR400) Polyquaternium 10 0.3 — — — — (JR125) Guar — — — 0.25 0.5Hydroxypropyltrimonium Chloride Dimethicone — 0.5 — — — DMDM Hydantoin0.2 0.2 0.2 0.2 0.2 Water qs 100 qs 100 qs 100 qs 100 qs 100 (1)Available under the tradename Varisoft 110 from Sherex Chemical Co.(Dublin, Ohio, USA) (3) Available under the tradename Adogen 442-110Pfrom Witco Corporation (Dublin, Ohio, USA) (5) Available under thetradename Armocare EQ-S from Akzo-Nobel Chemicals Inc. (Chicago,Illinois, USA)

What is claimed is:
 1. A styling shampoo composition comprising: (a)from about 5% to about 50% by weight of the composition of a detersivesurfactant, wherein the detersive surfactant is selected from the groupconsisting of a combination of anionic and zwitterionic surfactant, acombination of anionic and amphoteric surfactant, and a combination ofanionic, zwitterionic and amphoteric surfactants, wherein thezwitterionic and amphoteric surfactants have an attached group that isanionic at the pH of the composition; (b) from about 0.025% to about 3%by weight of the composition of an organic cationic deposition polymerwhich has a cationic charge density of from about 0.2 meq/gm to about 7meq/gm and, an average molecular weight of from about 5,000 to about 10million; (c) from about 0.1% to about 10% by weight of the compositionof a water-insoluble hair styling polymer; (d) from about 0.1% to about10% by weight of the composition of a volatile, water-insoluble solventfor the hair styling polymer; (e) from about 0.05% to about 5% by weightof the composition of a cationic spreading agent, selected from thegroup consisting of quaternary ammonium compounds, quaternary aminocompounds, and mixtures thereof, wherein the cationic spreading agenthas from two to four N-radicals, and the N-radicals arehydrophile-containing radicals having nonionic hydrophilic moietiesselected from the group consisting of alkoxy, polyoxyalkylene,alkylamido, hydroxyalkyl, alkylester moieties, and mixtures thereof; and(f) from about 22% to about 94.3% by weight of the composition water. 2.The composition of claim 1 wherein the detersive surfactant is selectedfrom the group consisting of a combination of anionic and amphotericsurfactants, and a combination of anionic and zwitterionic surfactants.3. The composition of claim 2 wherein the anionic surfactant is selectedfrom the group consisting of ammonium lauryl sulfate, ammonium laurethsulfate, alkyl glyceryl ether sulfonate, and mixtures thereof; theamphoteric surfactant is selected from the group consisting oflauroamphoacetate, lauroamphodiacetate, cocoamphoacetate,cocoamphodiacetate, and mixture thereof; and the zwitterionic surfactantis a betaine surfactant.
 4. The composition of claim 1 wherein thecomposition comprises from about 0.1% to about 2% by weight of theorganic cationic deposition polymer having a cationic charge density offrom about 0.6 meq/g to about 2.0 meq/g.
 5. The composition of claim 1wherein the organic cationic deposition polymer is selected from thegroup consisting of cationic cellulose derivatives, cationic starchderivatives, cationic guar gum derivatives, and mixtures thereof.
 6. Thecomposition of claim 5 wherein the cationic cellulose derivative isPolyquatemium-10.
 7. The composition of claim 1 wherein the compositioncomprises from about 0.5% to about 5% of the water-insoluble hairstyling polymer.
 8. The composition of claim 1 wherein thewater-insoluble hair styling polymer is an organic styling polymerselected from the group consisting of t-butyl acrylate/2-ethylhexylacrylate copolymers having a weight/weight ratio of monomers selectedfrom the group consisting of about 95/5, about 90/10, about 80/20, about70/30, about 60/40, and about 50/50; t-butyl acrylate/2-ethylhexylmethacrylate copolymers having a weight/weight ratio of monomersselected from the group consisting of about 95/5, about 90/10, about80/20, about 70/30, about 60/40, and about 50/50; t-butylmethacrylate/2-ethylhexyl acrylate copolymers having a weight/weightratio of monomers selected from the group consisting of about 95/5,about 90/10, about 80/20, about 70/30, about 60/40, and about 50/50;t-butyl methacrylate/2-ethylhexyl methacrylate copolymers having aweight/weight ratio of monomers selected from the group consisting ofabout 95/5, about 90/10, about 80/20, about 70/30, about 60/40, andabout 50/50; t-butyl ethacrylate/2-ethylhexyl methacrylate copolymershaving a weight/weight ratio of monomers selected from the groupconsisting of about 95/5, about 90/10, about 80/20, about 70/30, about60/40, and about 50/50; vinyl pyrrolidone/vinyl acetate copolymershaving a weight/weight ratio of monomers selected from the groupconsisting of about 10/90, and about 5/95; and mixtures thereof.
 9. Thecomposition of claim 1 wherein the water-insoluble hair styling polymeris a silicone grafted polymer selected from the group consisitng of: (i)t-butylacrylate/t-butyl-methacrylate/2-ethylhexyl-methacrylate/PDMSmacromer-20,000 molecular weight macromer 31/27/32/10; (ii)t-butylmethacrylate/2-ethylhexyl-methacrylate/PDMS macromer-15,000molecular weight macromer 75/10/15; (iii)t-butylmethacrylate/2-ethylhexyl-acrylate/PDMS macromer-10,000 molecularweight macromer 65/15/20; (iv)t-butylacrylate/2-ethylhexyl-acrylate/PDMS macromer-14,000 molecularweight macromer 77/11/12; (v)t-butylacrylate/2-ethylhexyl-methacrylate/PDMS macromer-13,000 molecularweight macromer 81/9/10; and (vi) and mixtures thereof.
 10. Thecomposition of claim 1 wherein the composition comprises from about 1%to about 6% of the water-insoluble volatile solvent having a boilingpoint from about 100° C. to about 200° C.
 11. The composition of claim 1wherein the water-insoluble volatile solvent is selected from the groupconsisting of dodecane, isododecane, isotetradecane, isohexadecane,2,5-dimethyldecane, diethyl succinate, dimethyl succinate, diethylmalonate, dimethyl malonate, cyclomethicone, and mixtures thereof. 12.The composition of claim 1 wherein the composition comprises a weightratio of the water-insoluble hair styling polymer to the water-insolublesolvent of from about 30:70 to about 60:40.
 13. The compositions ofclaim 1 wherein the cationic spreading agent is selected from the groupconsisting of ditallowamidoethyl hydroxypropylmonium methosulfate,dihydrogenated tallowamidoethyl hydroxyethylmonium methosulfate,ditallowamidoethyl hydroxyethylmonium methosulfate, di(partiallyhardened soyoylethyl) hydroxyethylmonium methosulfate, and mixturesthereof.
 14. The composition of claim 13 wherein the cationic spreadingagent is dihydrogenated tallowamidoethyl hydroxyethylmoniummethosulfate.
 15. The composition of claim 1 wherein the compositioncomprises from about 0.2% to about 1% of the cationic spreading agent.16. The composition of claim 1 wherein the composition further comprisesa non-volatile silicone conditioning agent selected from the groupconsisting of polyarylsiloxanes, polyalkyl siloxanes,polyalkylarylsiloxanes, derivatives thereof, and mixtures thereof. 17.The composition of claim 18 wherein the composition comprises from about0.1% to about 3% by weight of a non-volatile polydimethylsiloxaneconditioning agent.